CN101080511A - Method and apparatus for forming a thin-film solar cell using a continuous process - Google Patents

Method and apparatus for forming a thin-film solar cell using a continuous process Download PDF

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CN101080511A
CN101080511A CNA2005800433859A CN200580043385A CN101080511A CN 101080511 A CN101080511 A CN 101080511A CN A2005800433859 A CNA2005800433859 A CN A2005800433859A CN 200580043385 A CN200580043385 A CN 200580043385A CN 101080511 A CN101080511 A CN 101080511A
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layer
equipment
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约翰·R·塔特尔
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Daystar Technologies Inc
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Daystar Technologies Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1876—Particular processes or apparatus for batch treatment of the devices
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/568—Transferring the substrates through a series of coating stations
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention relates to new methods for manufacturing photovoltaic devices and an apparatus for practicing those methods of manufacture. The present invention employs a transfer-through system for advancing work piece substrates through an integrated apparatus of multiple treatment chambers that control each of the manufacturing processes.

Description

Be used to use successive processes to form the method and apparatus of thin-film solar cells
The cross reference of related application
The application's case is advocated the right of priority of the 60/626th, No. 843 U.S. Provisional Patent Application case of application on November 10th, 2004.
Technical field
The present invention that this paper discloses relates generally to photoelectric field, and relates to the thin-film solar cells of using successive processes to make thin-film solar cells and make according to described process or rather.
Background technology
Photoelectricity (PV) battery, module and energy resource system for the whole world to electric power day by day the expansible demand cleaning, reliable, renewable energy are provided.Regrettably, product cost fails fully to reduce to open key market at developing world always, at developing world, the demand of electric power is ordered about its use can pollute, nonupdatable source, for example coal and oil.Along with population expansion and the growth of energy expenditure per capita, discordant future is just being moved towards in the whole world, and when the time comes, energy requirement and supply will irreversibly be led to divergence.
The PV battery provides a kind of substitute for nonupdatable energy source.Yet, though can under lab make PV battery relatively efficiently, prove, be difficult to described technological development is become to have the commercial size technology of vital reproducibility and efficient for commerce existence.Owing to lack thin film fabrication technology efficiently, make the PV battery can't replace other energy source on the market effectively.
Use at present the rapid batch processing of multistep to make battery, wherein between each reactions steps, shift each product parts, and this type of shifts comparatively loose and need react in indoor circulation.Typical process is made up of a series of discrete batch processings chamber, and each treatment chamber designs at the formation of each layer in the battery especially.A shortcoming of this process is that substrate is passed vacuum back again in for several times from the vacuum transfer to the air.The alternate system uses a series of discrete batch processings chamber, and itself and the coupling of rolling successive processes are to be used for each chamber.The main drawback of this process is the discontinuity of system and needs to destroy vacuum.
Use aforesaid method, one or more defective may make whole plate (single assembly) use, and causes that unitary zero yield of product.These and other problem makes thin film technique only account for the whole world less than 10% the market share.
Summary of the invention
The invention provides a kind of photovoltaic of producing in the following manner: provide and pass series of reaction and be installed to substrate on the pallet, in described reaction chamber, can on described pallet, form blocking layer, bottom contact layer, one or more semiconductor layers, n type knot buffer layer, intrinsic transparent oxide layer, oxidic, transparent, conductive layers and top metal grid sequentially.
In alternate embodiment of the present invention, use continuous manufacturing processed to form thin-film solar cells.In this embodiment, handle flexibility and successive substrate by reactor, described reactor has a plurality of treatment zones, and described treatment zone is settled along the inlet of reactor and the continuous path between the outlet.Each treatment zone in the reactor is defined by predetermined processing environment, and is exclusively used in the formation of a step layer of device.Each zone can further comprise the treatment condition that combine with one or more deposition methods.
Further disclose a kind of method that is used for forming in a continuous manner optoelectronic equipment.In this embodiment, make continuous substrate by having the reactor of a plurality of treatment zones, wherein the production step stage of each region-specific in device is made with set rate.These production stages comprise: the loading or the area of isolation that 1) are used to prepare substrate; 2) be used for the environment of deposited barrier layer; 3) be used to deposit the environment of bottom contact layer; 4) be used for the environment of depositing semiconductor layers; 5) be used to deposit the environment of basic material; 6) be used to deposit the environment of other semiconductor layer; 7) be used for one or more environment of heat-treating to above-mentioned layer; 8) be used to deposit the environment of n type semiconductor layer, wherein this one deck serves as the knot buffer layer; 9) be used for the environment of deposition intrinsic transparent oxide layer; With 10) be used for the environment of the transparent oxide layer of depositing electrically conductive.In a further embodiment, described process can so that make the thin-film solar cells with less layer, perhaps also can be added extra processing through adjusting to comprise less zone.
Should also be clear that and to use extra zone that deposition or treatment zone are isolated from each other, in case chemical cross-contamination and permission optimal recovery.These area of isolation can change in the process that workpiece resides therein, and reach optimum with the substrate that allow to expose, and make next production stage that carries out in the vacuum-sealing can prevent crossed contamination.
According to specific photoelectricity design, can adjust one or more zones in the reactor.For instance, one or more zones that comprise compatible sedimentary environment capable of being combined.Perhaps, the zone can comprise the combination of the deposition process of the sedimentary environment that can use variation or subregion.
In another embodiment, one or more layers can be combined into single layer and it is deposited in the single zone.For instance, semiconductor layer and basic material can be made up to form alkaliferous mixed phase semiconductor source layer.
Description of drawings
Fig. 1 shows the embodiment of the thin-film solar cells of producing by production technology of the present invention.
Fig. 2 shows the embodiment that is used to make the successive processes of thin-film solar cells according to of the present invention.
An embodiment of substrate is presented in Fig. 3 explanation from left to right in successive processes according to the present invention.
Fig. 4 explanation is according to an embodiment of successive processes of the present invention.
Fig. 5 explanation is according to another embodiment of successive processes of the present invention, and wherein each zone further comprises one or more subregions.
The embodiment of Fig. 6 A method for displaying and processing wherein presents and handles two substrates simultaneously by sequential sputter-evaporate process according to the present invention.
Two substrates are wherein presented and handle to the vertical view of the embodiment of Fig. 6 B method for displaying and processing simultaneously by sequential sputter-evaporation/sputter-evaporate process.
For the sake of clarity, each all comprises reference number in graphic.These reference numbers are abideed by general naming method.Reference number will have three or four numerals.Previous or two digitized representations use the figure number of reference number first.For instance, at first the reference number that uses in figure one will have the numeral as 1XX, and the numeral of at first using in figure five will have the numeral as 5XX.Thereafter the particular artifact in two digital representative diagram.An object among Fig. 1 will be 101, and another object will be 102.The same reference numbers of using in figure is subsequently represented same item.
Embodiment
The present invention uses a kind of new production unit so that produce optoelectronic equipment.Specific equipment will depend on specific optoelectronic equipment design, and it can change.Fig. 1 shows optoelectronic equipment or thin-film solar cells 100, and it comprises substrate 105, blocking layer 110, bottom contact layer 120, semiconductor layer 130, basic material 140, second half conductor layer 150, n type knot buffer layer 160, intrinsic transparent oxide layer 170 and transparent conductive oxide layer 180.Those skilled in the art will realize that thin-film solar cells can comprise less layer and still plays a role according to the present invention.For instance, device does not need to have basic material.
Two kinds of versions of integrated production unit are provided.In each case, provide a series of treatment chambers, wherein each chamber provides specific system for handling, handles so that form specific layer deposition or layer.The workpiece that in these treatment chambers each all allows a member will just be manufactured into optoelectronic equipment transmits a plurality of chambers of passing through in proper order from the chamber of first design, till workpiece being manufactured the photovoltaic stack of design.
These a plurality of reaction or treatment chambers that possess transport sector also can comprise one or more insulated chambers, and it guarantees to keep especially effectively reactant in the chamber that needs especially, and can not pollute downstream process.Certainly, this isolated system is particularly important when forming the semiconductor layer of optoelectronic equipment, and wherein the material of relatively small amount determines that layer is p type or n N-type semiconductorN.This carrier is configurable to be had with reference to member, in the position of defining workpiece is positioned in the generation equipment guaranteeing.
The present invention imagines two types being used for the transport sector of workpiece transfer by equipment.First kind is the continuous rolling system, wherein makes the substrate of relative flexibility run through system and it is collected.Finish pile up after, substrate can be divided into a plurality of aliquots, perhaps, if photovoltaic stack design allows, can be with its collection on the spool of finishing.
Second method is to provide a plurality of workpiece substrates on device, and described device can be clamped to substrate on the carrier, and described carrier also has and allows part to advance with accurate way to pass the member of production unit.
Referring to Fig. 1, all layers all are deposited on the substrate 105, and substrate 105 can comprise one in a plurality of functional materialss, for example glass, metal, pottery or plastics.Directly be deposited on the substrate 105 is blocking layer 110.Blocking layer 110 comprises thin conductor or extremely thin insulating material, and in order to stop that undesirable element or compound are out-diffusion to the rest part of battery from substrate.This blocking layer 110 can comprise chromium, titanium, silicon oxide, titanium nitride and the associated materials with required electroconductibility and tolerance.Next sedimentary layer is a bottom contact layer 120, and it comprises non-reactive metal, for example molybdenum.Next is deposited upon on the contact layer 120 of bottom, and is p type semiconductor layer 130, so that improve the adhesivity between absorber layers and the bottom contact layer 120.P type semiconductor layer 130 can be I-III A, bThe same N-type semiconductorN of-VI, but preferred composition is any one the alloy in Cu:Ga:Se, Cu:Al:Se or Cu:Tn:Se and the aforesaid compound.
In this embodiment, the formation of p type absorber layers comprises the phase mutual diffusion of a plurality of discrete layers.Finally as shown in Figure 1, p type semiconductor layer 130 and 150 is combined into one composite bed 155, and it serves as the main cartridge of sun power.In this embodiment, add basic material 140 and sow, and increase the carrier concentration and the grain size of absorber layers 155, thereby improve the efficiency of conversion of solar cell with the growth that is used to succeeding layer.
Basic material 140 generally is based on sodium, and usually with Na-VII (VII=F, Cl, Br) or Na 2The form deposition of-VI (VI=S, Se, Te).When deposition, basic material 140 can adopt the form of Na-A:I-III-VI alloy (A=VI or VII), to allow and semiconductor layer 150 commutative elements.
As shown in Figure 1, basic material disperses, and above semiconductor layer 150 is deposited on.Yet it is discrete that basic material can't keep, but absorbed the part in the formation that becomes the final p type absorber layers shown in 155 by semiconductor layer 150.When deposition, basic material by known other deposition of evaporation, sputter or those skilled in the art on the p type semiconductor layer 130 or on other layer that is pre-existing in.In a preferred embodiment, basic material 140 (is preferably 10 at ambient temperature and in appropriate vacuum -6To 10 -2Holder) stands sputter.In case, just under about 400 ℃-600 ℃ temperature, described layer is heat-treated through deposition.
After thermal treatment, proceed photovoltaic production process by deposition n type knot buffer layer 160.This layer 160 interacts final and absorber layers 155, to form necessary p-n junction 165.Next the native oxide layer 170 of deposit transparent is to serve as the heterojunction with CIGS cartridge.At last, the transparent oxide layer 180 of depositing electrically conductive is to serve as the top of battery electrode.This last one deck conducts electricity, and can be with the electric current carrying to the grid carrier, and described grid carrier allows to take away the electric current that is produced.
Fig. 2 schematically shows the reactor 200 that is used to form solar cell.Reactor is from left to right presented and passed to substrate 205 via feed roller 215 and absorption roller 260.Reactor 200 comprises one or more treatment zones, and it is expressed as 220,230,240 and 250 in Fig. 2, and wherein each treatment zone includes the environment that is used for deposition material on substrate 205.Described zone mechanically or operationally is connected to each other in reactor 200.As used herein, term " environment " is meant the condition curve that is used on substrate 205 deposition or the reaction wood bed of material or material blends when substrate 205 is arranged in the specific region.
Dispose each zone according to layer just processed in the solar cell.For instance, a zone can be configured to carry out the sputter operation, wherein comprises heating source and one or more source targets.
Preferred situation is to make the substrate 205 of elongation by various treatment zones with controllable speed.Expect that also substrate 205 can have 0.5 meter/minute to about 2 meters/minute translatory velocity.Therefore, consider required transmission speed, the material residence time near specific source materials, preferably the process of tuning each intra-zone is to form required cross section.Therefore, consider the residence time of determining by transmission or translatory velocity of piling up, can select the feature (for example material and process selection, temperature, pressure or sputter transfer rate etc.) of each process, to guarantee to transmit in a suitable manner composition material.
According to the present invention, can the continuous rolling mode with substrate 205 transmission by described process, perhaps with substrate 205 with the assembling of " picture frame " type to be placed on mode on the pallet and to transmit and to transmit by described process with transposition, back a kind of mode has been described among Fig. 3.Referring to Fig. 3, a substrate or one group of substrate 310 are installed on the pallet 320, described pallet 320 translations are by one or more zones 330 and 340 on the track 350.In alternate embodiment, described process can further comprise second substrate or the second group of substrate that is placed to 310 one-tenth back-to-back configurations of substrate.
Expect that the background pressure scope in the various zones will hold in the palm the 10-3 holder from 10-6.Can realize being higher than the pressure of benchmark vacuum (10-6 holder) by adding pure gass such as argon gas, nitrogen or oxygen for example.Preferred situation is, speed R is a constant, so that substrate 205 201 is not advanced with not stopping and passed reactor 200 and arrive outlet 202 from entering the mouth.Be understood by those skilled in the art that, can therefore on substrate 205, form solar cell stack in a continuous manner, and need not to make substrate 205 in reactor 200, to stop.
Reactor among Fig. 2 can further comprise vacuum isolation sub-zones or slit valve (slit valve), and it is configured to isolate adjacent treatment zone.Provide vacuum isolation sub-zones or slit valve so that between different pressure environments, transmit substrate continuously.
Reactor 200 among Fig. 2 is a plurality of N treatment zones 220,230,240 and 250.Yet, it will be understood by one of ordinary skill in the art that reactor can comprise zone 220,230,240,250 ... the n-quadrant.Load/unload zone 210/211 comprises and can isolate with the rest part of reactor and can be to the zone of atmosphere opening.
According to the present invention, above-mentionedly comprise that ten layers solar cell can use the reactor that comprises ten zones to make, wherein each zone comprises the environment that is used to deposit this certain layer.Yet, in each embodiment, various zones capable of being combined, thereby the sum in the zone that reduction reactor 200 contains.
Fig. 2 shows that each zone can comprise that in each embodiment discrete environment is to be used to deposit certain layer; Two zones 220,230 are combined into a zone that is illustrated by the broken lines 270, to make up a plurality of processes aspect.According to the structure of required solar cell, any variation can take place in the number of regions that reactor contains.In this embodiment, substrate 205 is through zone 220,230,240 and 250, and described zone is carried out respectively and handled operation 221,231,241 and 251.
In a preferred embodiment, described process can further comprise substrate 215, and itself and substrate 205 are back-to-back advanced.In this embodiment, substrate 215 and 205 is with back-to-back configuration vertical orientation, and through zone 220,230,240 and 250, it carries out identical processing operation 222,232,242 and 252.
Fig. 4 displaying is from left to right presented substrate 410 via feed roller 420 and absorption roller 430 by reactor 400.In this example, reactor comprises three treatment zones 440,450 and 460.In reactor 400, zone 440 is configured to carry out the sputter operation, wherein comprises heating source 441 and one or more source targets 442.Equally, zone 460 is configured to carry out the sputter operation, and it comprises nozzle 461 and target 462.Zone 450 is configured to carry out the sputter operation, and it comprises nozzle 451 and target 452.Zone 450 is configured to carry out hot evaporate process.
Fig. 4 schematic presentation is configured to isolate the vacuum insulation zone 470 and 480 of adjacent treatment zone.Provide described vacuum insulation zone so that between the different pressures environment, transmit substrate continuously.Specifically, be used for to use area of isolation between the chamber of SEDIMENTARY SELENIUM.
Reactor 400 shown in Figure 4 comprises suction system, is used to form the pressure that is lower than minimum processing pressure.The sputter zone can have 10 -3The pressure of holder, and thermal region can have 10 -6The pressure of holder.In this example, area of isolation can have 10 -7The pressure of holder is so that provide effective low pressure to stop.
The lower pressure of area of isolation is configured to the minimum conduction flow between the zone, thereby provides metastable environment in adjacent treatment zone.The hole that material moves through is preferred slightly greater than the thickness of substrate, so that will enter the minimum gas flow in the insulated chamber, still keeps part flow simultaneously.
The length of area of isolation can be determined by some factors: the internal pressure environment of adjacent area; The residence time of workpiece in the chamber; Working process is for the susceptibility of the crossed contamination between the reactor area or the like.
The storer 490 that reactor illustrated in fig. 4 preferably comprises microprocessor, be associated and being used to is controlled the transmitter of the operation of the process that is disclosed.Become known for storing, obtain and carry out computer under microprocessor 490 can comprise in the field, perhaps can be the common industrial control unit (ICU) that is enough to be used for monitoring and controlling treatment variable limited, predetermined group about the computer instruction of the operation of handler.
Computer 490 operationally is coupled to each transmitter in each zone, adjusts desired parameter corresponding to the feedback of all respects of process and in response to the feedback that receives with reception.For instance, reactor 400 can comprise and is placed in the transmitter 443 of zone in 440, is placed in the transmitter 453 in the zone 450 and is placed in transmitter 463 in the zone 460.One or more transmitters can be placed in each zone to provide desired environmental feedback to computer 490.These transmitters can monitor the variable as the object features on vapor pressure, steam content, temperature, workpiece translational motion speed, surface etc.
But the envrionment conditions in the subregion in the temperature and pressure of sensing given area and given area or zone.For instance, can provide extra transmitter 454 particular sub-area with the zone 450 of 453 sensings of detection sensor.In this way, can in the zone, provide a plurality of environment.For instance, transmitter can be configured to the temperature curve that provides different in same area.
In addition, the others of the process that is disclosed also can be come sensing and control by dynamical fashion.For instance, can dispose tension pick-up during the course, dynamically to keep the tension force of being wanted on the substrate.When the specific part of substrate was mobile towards downstream during the course, it may experience temperature variation.This will cause substrate to expand because of the effect of the temperature of variation naturally and shrink.In order to ensure substrate being maintained under the constant tension force, transmitter can provide feedback to computer, and computer can be configured to control in response to the feedback that senses and presents and absorb roller or other feed mechanism.For example the parameter of temperature or sputter power can and/or be adjusted to keep desired tension force through dynamic sensing.
In addition, the expection substrate can be configured to make that tension force can be subjected to accurate control.For instance, can be intentionally that the part near one or two edge in the substrate is exposed, so that roller guiding piece, tension force control or other feed mechanism directly contact and therefore control the tension force of substrate.Perhaps, tractor feed guide holes, for example the guide hole that generally has in paper or film is placed in around the substrate so that transmission and tension control.
But these mechanical tension control method combining environmental transmitters use, so that control the tension force of substrate more accurately when an environment is passed to next environment at substrate.
Fig. 6 A shows the top view illustration of a part of handling the reactor 600 of substrate 601 and 602 in back-to-back mode, and also explanation by regional 611 isolated sequential sputter-evaporate process.In order to realize back-to-back processing, be the heating source 607 of substrate 602 with heating source 603 mirrors of substrate 601.Equally, sputter source 604, heating source 605 and vapor deposition source 606 mirrors with substrate 601 are sputter source 607, heating source 609 and the vapor deposition source 610 of substrate 602.
Fig. 6 B shows with the top view illustration of back-to-back mode with the part of the reactor 620 of sequential sputter-evaporation/sputter-evaporate process processing substrate 621 and 622.As shown in Fig. 6 A, be the sputter source 628 of substrate 622 with sputter source 622 mirrors of substrate 621.Equally, with the heating source 623 and 626 of substrate 621, vapor deposition source 624 and 627 and vapor deposition source 625 mirrors be the heating source 629 and 632, vapor deposition source 630 and 633 and sputter source 631 of substrate 622.Therefore, by the simple repetition of heating and material source, can be in identical machine that the output of solar cell is double effectively.
Concrete treatment step
Turn to indivedual process steps now, described process begins load substrates and makes it by isolated loading area or similar units 210.In each embodiment, reactor 200 contains area of isolation 210.Perhaps, area of isolation 210 can be attached to the external portion of reactor 200.First treatment zone 210 can further comprise substrate preparation environment, with the flaw of any remnants of the atom level of removing the surface.Substrate preparation can comprise: ionic fluid, deposition, heating or sputter-etch.
Second treatment zone can be and is used for depositing the environment that is used for the isolated blocking layer of substrate impurity, and wherein the blocking layer provides conductive path between substrate and succeeding layer.In a preferred embodiment, the blocking layer comprises the element such as for example chromium or titanium etc. that is transmitted by the sputter process.Preferable case is, described environment comprises under the envrionment temperature about 10 -3Hold in the palm about 10 -2Pressure in the holder scope.
The 3rd treatment zone in elder generation forefoot area downstream comprises the environment that is used to deposit as the metal level of bottom contact layer.The bottom contact layer is included as the thickness that electric current provides conductive path.In addition, the bottom contact layer is as first conductive layer of solar cell stack.Described layer can be used for further preventing that chemical compound such as impurity for example is diffused into the rest part of solar battery structure from substrate, perhaps as the thermal expansion cushion between the rest part of lining back layer and solar battery structure.Preferable case is, the bottom contact layer comprises molybdenum, yet the bottom contact layer can comprise other conducting metal, for example aluminium, copper or silver.
The 4th zone is provided for depositing the environment of p type semiconductor layer.Described p type semiconductor layer can be used as the epitaxial template of cartridge growth.Preferably situation is, the p type semiconductor layer is a homotype I-IIIVI2 material, and wherein the optical band gap of this material is higher than the optical band gap of p type absorber layers.For instance, semiconductor layer can comprise any one the alloy in Cu:Ga:Se, Cu:Al:Se or Cu.Tn:Se and the aforesaid compound.Preferred situation is to transmit described material by the sputter process from envrionment temperature under about 300 ℃ temperature under the background pressure of 10-2 holder at 10-6.Preferred situation is that temperature range is to about 200 ℃ from envrionment temperature.
The 5th zone in elder generation forefoot area downstream is provided for depositing basic material with the growth that strengthens described types of absorbent body and the environment of electrical property.Preferred situation is, holds in the palm sputter Seed Layer under the pressure range that 10-2 holds in the palm at ambient temperature and at about 10-6.Preferably situation is, described material comprises compounds such as NaF, Na2Se, Na2S or KCI, and wherein thickness range is to about 500nm from about 50nm.
The 6th zone in elder generation forefoot area downstream can comprise the environment that is used to deposit the additional semiconductor that is used for the CIGS absorber layers.In a preferred embodiment, the 6th zone can comprise further that one or more are used for the subregion of depositing semiconductor layers.In one embodiment, the CIGS absorber layers forms in the following manner: at first transmit precursor material in one or more continuous subregions, make the precursor material reaction become p type absorber layers then in the downstream heat treatment zone.Therefore, particularly for the CIGS system, in the form of layer, can there be two material deposition steps and the 3rd heat treatment step.
In precursor delivery zones, the precursors to deposit material layer wherein comprises evaporation, sputter and chemical vapour deposition or its combination in many ways.Preferable case is to transmit precursor material under about 200 ℃-300 ℃ temperature range.Need make the precursor material reaction to form p type cartridge as far as possible apace.As before at this point as described in, precursor layer can be formed the mixture of thin layer or form a series of thin layers.
Manufacturing installation also can have the 7th treatment zone in previous treatment zone downstream, and it is used for one or more previous layer are heat-treated.Term " polynary thing " comprises binary thing, ternary thing etc.Preferable case is that thermal treatment makes previous nonreactive element or polynary thing react.For instance, in one embodiment, Cu, the In, Se and the Ga that preferably have the various ratios of the multi-element compounds that is various array configurations and has element are as the source that is deposited on the workpiece.Reaction environment comprises into the selenium and the sulphur of different ratios, and temperature range is from about 400 ℃ to about 600 ℃, has or do not have the background inert gas environment.In various embodiments, can the treatment time be minimized to one minute by the hybrid mode of optimizing precursor or still less.Optimum pressure in the environment depends on that environment is reactive or inert.According to the present invention, in thermal treatment zone, pressure range is from about 10 -6To about 10 -2Holder.Yet, it should be noted that these scopes depend on the reactor design in stage as a whole, the planner of optoelectronic equipment and the operational variable of equipment to a great extent.
Reactor can have the 8th treatment zone that is used to form the n type semiconductor layer or the body of going with.The knot buffer layer is from II-VI or III XSelect in the VI family.For instance, the knot buffer layer can comprise by the sedimentary ZnO of evaporation, distillation or chemical gaseous phase depositing process, ZnSe, ZnS, In, Se or InNS.Temperature range is from about 200 ℃ to about 400 ℃.
In addition, described process also can have the 9th zone, and it has the environment of the intrinsic layer that is used for deposit transparent oxide compound (for example ZnO).According to the present invention, described intrinsic transparent oxide layer can deposit by several different methods, wherein including (for example) RF sputter, CVD or MOCVD.
In each embodiment, described process also can have the tenth zone, and it has and is used for the deposit transparent conductive oxide layer with the environment as the top electrodes of solar cell.In one embodiment, for instance, the ZnO of aluminium is arranged with the sputtering way dopant deposition.Preferable case is that described environment comprises the pressure of about 200 ℃ temperature and about 5 millitorrs.Perhaps, can use ITO (tin indium oxide) or analogue.
As mentioned above, in one embodiment, reactor can comprise discrete zone, and wherein each zone is corresponding to the formation of one deck of optoelectronic equipment.Yet in a preferred embodiment, the sum in the zone in the reactor is reduced in the zone that comprises similar composition and/or envrionment conditions capable of being combined therefore.
For instance, in Fig. 5, the zone 510 comprises subregion 511 and 512, and zone 515 comprises subregion 516 and 517, and zone 520 comprises a zone, and wherein each zone and subregion comprise predetermined environment.In this example, can be in subregion 511 deposition material A, and can in subregion 512, deposit different material B, wherein the environment of the subregion 512 in materials A downstream is different from the environment in the subregion 511.Therefore, substrate 505 can experience different temperature or other conditional curve when in the different zones of same area 510.According to this embodiment, the zone can be defined as has predetermined pressure, and the zone can comprise one or more zones, subregion or stage wherein, and wherein each subregion is configured to make in identical pressure environment institute's material of wanting to deposit or reacts.
Then, substrate 505 can be delivered to chamber 515, deposition material C in subregion 516 wherein, and in subregion 517 deposition material D.Finally, substrate 505 arrives zone 520, deposits single material E therein.
Be understood by those skilled in the art that, reactor 500 can have as described along the path that the translation of substrate is defined be placed in reactor inlet and the outlet between a series of zones.In each zone, can provide one or more to form environment or subregion, so that selected target material deposits or reaction, thereby be formed for forming the successive processes of solar cell stack.In case substrate enters reactor, each of solar stack layer just deposits and forms in mode in proper order, and wherein each downstream process of successive is used to form solar cell stack, provides till the thin-film solar cells of finishing up to the exit at reactor.
Though showed and described the embodiment and the application of this disclosure, it will be apparent to those skilled in the art that under the situation of the inventive principle that does not depart from this paper, may there be modification and improvement far more than foregoing.Therefore, this disclosure is not subjected to any restriction except the spirit of appended claims.

Claims (56)

1. equipment that is used to make optoelectronic equipment, it comprises and is used for substrate is provided to member with lower area continuously:
Can be provided for the zone of the environment of layer behind the depositing electrically conductive;
Can be provided for depositing the zone of the environment of p type semiconductor layer;
Can be provided for depositing the zone of the environment of n type semiconductor layer; With
Can be provided for the zone of the environment of deposit transparent conduction anterior layer.
2. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises and is used for substrate being provided to a plurality of reactor area so that prepare the member of described substrate successively.
3. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises first treatment zone, described zone can be provided for described substrate is moved to from surrounding environment the environment of processing environment.
4. equipment according to claim 3, wherein said substrate partly or integrally move to the reduction pressure that conforms to the subsequent disposal environment from barometric point.
5. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for deposited barrier layer.
6. equipment according to claim 5, wherein said blocking layer comprise slim conductor or extremely thin insulating material.
7. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing electrically conductive bottom contact layer.
8. equipment according to claim 7, wherein the deposition of conductive bottom contact layer comprises metal level.
9. equipment according to claim 8, wherein said metal level comprise the conducting metal of selecting from the group that is made of molybdenum, titanium, tantalum and other acceptable metal or alloy.
10. equipment according to claim 9, wherein said metal level are molybdenum.
11. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing basic material.
12. equipment according to claim 11, wherein said basic material are Na-VII or Na 2-VII.
13. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing semiconductor layers.
14. equipment according to claim 13, wherein said semiconductor layer comprise I, III, VI family element.
15. equipment according to claim 14, wherein said semiconductor layer comprises CuGaSe 2, CuAlSe 2Or CuInSe 2With the one or more alloy in described I, III, the VI element.
16. equipment according to claim 15, wherein said semiconductor layer comprises CuGaSe 2
17. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing extra semiconductor layer, and wherein said semiconductor layer comprises precursor p type absorbent material.
18. equipment according to claim 17, wherein said precursor material comprise I, III, VI family element.
19. equipment according to claim 18, wherein said precursor material comprise I-(IIIa, IIIb)-VI 2Layer.
20. equipment according to claim 19, wherein said precursor material comprise I-(IIIa, IIIb)-VI 2One or more in the element of layer, 0.0＜IIIb/ (IIIa+IIIb)＜0.4 wherein.
21. equipment according to claim 19, wherein said precursor material comprise I-(IIIa, IIIb)-VI 2One or more in the alloy of layer, 0.0＜IIIb/ (IIIa+IIIb)＜0.4 wherein.
22. equipment according to claim 1, wherein said semiconductor layer comprises the CIGS absorber layers, and it comprises In 1-x: Ga x: Se 2, wherein the scope of x between 0.2 to 0.3, wherein thickness range from about 1 μ m to about 3 μ m.
23. equipment according to claim 22, wherein said CIGS absorber layers are to form by transmitting I, III and VI type precursor metal, wherein with Cu, In 1-x, Ga xAnd Se 2Layer sequential deposition is on described substrate.
24. equipment according to claim 22, wherein said CIGS absorber layers are to form by transmitting I, III and VI type precursor metal, wherein with Cu, In 1-x, Ga xAnd Se 2Layer sequential deposition and then synthesizes alloy mixture by thermal treatment with it on described substrate.
25. equipment according to claim 22, wherein said CIGS absorber layers are to form by transmitting I, III and VI type precursor metal, wherein synthetic separately Cu:Ga xLayer, and then with itself and In X-1Layer and Se 2Layer common deposited is on substrate.
26. equipment according to claim 22, wherein said CIGS absorber layers are to form by transmitting I, III and VI type precursor metal, wherein synthetic separately Cu:Ga xLayer, and then with itself and In 1-xLayer and Se 2Layer common deposited and then synthesizes alloy mixture by thermal treatment with it on substrate.
27. equipment according to claim 22, wherein said CIGS absorber layers are to form by transmitting I, III and VI type precursor metal, wherein synthetic separately Cu:Ga x: In X-1Layer, and then with itself and Se 2Layer common deposited is on substrate.
28. equipment according to claim 22, wherein said CIGS absorber layers are to form by transmitting I, III and VI type precursor metal, wherein synthetic separately Cu:Ga x: In X-1Layer, and then with itself and Se 2Layer common deposited and then synthesizes alloy mixture by thermal treatment with it on substrate.
29. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone that can be provided for environment that one or more layers are heat-treated.
30. equipment according to claim 29, wherein said processing occurs in from 10 -6Holder is in the temperature range of the pressure range of barometric point and 300 ℃ to 700 ℃.
31. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing the n type semiconductor layer.
32. equipment according to claim 31, wherein said n type semiconductor layer disperses.
33. equipment according to claim 32, wherein said discrete layer comprise one or more in II-VI, the III-VI family element.
34. equipment according to claim 32, wherein said discrete layer material comprise from by (In, Ga) yOne or more in the material of selecting in the group that (Se, S, O) and (Zn, Cd) (Se, S, O) forms.
35. equipment according to claim 32, wherein said discrete layer material comprise from by (In, Ga) 2Se 3, (In, Ga) 2S 3, one or more in the material selected in the group that forms of ZnSe, ZnS and ZnO.
36. equipment according to claim 32, wherein said n type semiconductor layer are to form by dopant species being diffused in the p type absorber layers.
37. equipment according to claim 36, wherein said dopant species are from by selecting the elementary composition group of one or more II or III family.
38. according to the described equipment of claim 37, wherein said dopant species comprises Zn or Cd.
39. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing the insulation transparent semiconductor layer.
40. according to the described equipment of claim 39, wherein said insulation transparent semiconductor layer comprises one or more materials in II-VI or the II-IV-VI family.
41. according to the described equipment of claim 39, wherein said insulation transparent semiconductor layer comprises one or more materials among ZnO or the ITO.
42. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises the treatment zone of the environment that can be provided for depositing electrically conductive transparent semiconductor layer.
43. according to the described equipment of claim 42, wherein said conductive, transparent semiconductor layer comprises one or more materials in II-VI or the II-IV-VI family.
44. according to the described equipment of claim 42, wherein said conductive, transparent semiconductor layer comprises ZnO, Cd 2SnO 4Or one or more materials among the ITO.
45. the equipment that is used to make optoelectronic equipment according to claim 1, it further comprises first treatment zone, and described zone can be provided for described substrate is got back to the environment of described surrounding environment from described processing environment translation.
46. according to the described equipment of claim 45, wherein said substrate partly or integrally moves to the reduction pressure that conforms to the subsequent disposal environment from barometric point.
47. a method that is used to make optoelectronic equipment, it comprises:
Workpiece is provided in proper order the 4th zone of the environment that can be provided for depositing semiconductor layers;
Described workpiece is provided in proper order the 5th zone of the environment that can be provided for depositing basic material; With
Described workpiece is provided in proper order the 6th zone of the environment that can be provided for depositing p type absorber layers precursor material.
48. according to the described method that is used to make optoelectronic equipment of claim 47, it comprises further substrate is provided to the equipment with a plurality of reactor area in proper order that wherein said first area is to be used to prepare the preparation of described substrate to produce the loading or the area of isolation of workpiece.
49. according to the described method that is used to make optoelectronic equipment of claim 47, it further comprises second reactor area that described workpiece is provided in proper order the environment that can be provided for deposited barrier layer.
50. according to the described method that is used to make optoelectronic equipment of claim 47, it further comprises the 3rd zone that described workpiece is provided in proper order the environment that can be provided for depositing the bottom contact layer.
51. according to the described method that is used to make optoelectronic equipment of claim 47, it further comprises the SECTOR-SEVEN territory that can provide the one or more environment of heat-treating in the previous layer is provided described workpiece in proper order.
52. according to the described method that is used to make optoelectronic equipment of claim 47, it further comprises the 8th treatment zone that described workpiece is provided in proper order the environment that can be provided for depositing the n type semiconductor layer, wherein this layer is as the knot buffer layer.
53. according to the described method that is used to make optoelectronic equipment of claim 47, it further comprises the 9th treatment zone that described workpiece is provided in proper order the environment that can be provided for the deposition intrinsic transparent oxide layer.
54. according to the described method that is used to make optoelectronic equipment of claim 47, it further comprises the tenth treatment zone that described workpiece is provided in proper order the environment that can be provided for the deposit transparent zone of oxidation.
55. an equipment that is used to make optoelectronic equipment, it comprises the member that is used for successively substrate being provided to a plurality of reactor area, and described a plurality of reactor area comprise:
Can be provided for described substrate is moved to the treatment zone of the environment of processing environment from surrounding environment, wherein said substrate partly or integrally moves to the reduction pressure that conforms to the subsequent disposal environment from barometric point;
Can be provided for the treatment zone of the environment of layer behind the depositing electrically conductive, the deposition of wherein said conductive bottom contact layer comprises the metal level of being made up of molybdenum;
Can be provided for the treatment zone of the environment of deposited barrier layer, wherein said blocking layer comprises slim conductor or extremely thin insulating material;
Can be provided for the treatment zone of the environment of depositing semiconductor layers, wherein said semiconductor layer comprises CuGaSe 2, CuAlSe 2Or CuInSe 2With the one or more alloy in I, III, the VI element;
Can be provided for depositing the treatment zone of the environment of basic material, wherein said basic material is Na-VII or Na 2-VII;
Can be provided for depositing the treatment zone of the environment of second half conductor layer, wherein said semiconductor layer comprises I-(IIIa, IIIb)-VI 2Layer;
Thereby the treatment zone of one or more layers being heat-treated the environment that forms p type absorber layers can be provided, and wherein said processing occurs in from 10 -6Holder is in the temperature range of the pressure range of barometric point and 300 ℃ to 700 ℃;
Can be provided for depositing the treatment zone of the environment of n type semiconductor layer, wherein said n type semiconductor layer comprises following group (InGa) yOne or more in (Se, S, O) or the following group (Zn, Cd) (Se, S, O);
Can be provided for the treatment zone of the environment of deposit transparent conduction anterior layer, wherein said insulation transparent semiconductor layer comprises one or more materials among ZnO or the ITO; With
Can be provided for the treatment zone of the environment of depositing electrically conductive transparent semiconductor layer, wherein said conductive, transparent semiconductor layer comprises ZnO, Cd 2SnO 4Or one or more materials among the ITO.
56. a method that is used to make optoelectronic equipment, it comprises:
The a plurality of substrate pieces that append to support element are provided to the equipment with a plurality of reactor area in proper order, its
Middle first area is to be used to prepare the preparation of described substrate to produce the loading or the area of isolation of workpiece;
Described workpiece is provided in proper order the second area of the environment that can be provided for deposited barrier layer;
Described workpiece is provided in proper order the 3rd zone of the environment that can be provided for depositing the bottom contact layer;
Described workpiece is provided in proper order the 4th zone of the environment that can be provided for depositing semiconductor layers;
Described workpiece is provided in proper order the 5th zone of the environment that can be provided for depositing basic material;
Described workpiece is provided to the 6th zone of the environment that can be provided for precursors to deposit p type absorbent material in proper order, and wherein said precursor p type absorber layers material comprises the alloy material based on copper indium two selenium;
Described workpiece is provided in proper order the SECTOR-SEVEN territory that can be provided for to the one or more environment of heat-treating in the previous layer;
Described workpiece is provided to the 8th treatment zone of the environment that can be provided for depositing n type compound semiconductor in proper order, and wherein this layer is as the knot buffer layer;
Described workpiece is provided in proper order the 9th treatment zone of the environment that can be provided for the deposition intrinsic transparent oxide layer; With
Described workpiece is provided in proper order the tenth treatment zone of the environment that can be provided for the depositing electrically conductive transparent oxide layer.
CNA2005800433859A 2004-11-10 2005-11-10 Method and apparatus for forming a thin-film solar cell using a continuous process Pending CN101080511A (en)

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